Branched ethylenic macromonomer and its polymer

ABSTRACT

There are herein disclosed a branched ethylenic macromonomer which can function as a comonomer to provide a copolymer having excellent molding and working properties and which can be hydrogenated to provide a hydrogenated product as a wax useful in various uses, a copolymer having the excellent molding and working properties obtainable by using this macromonomer as a comonomer, and a branched ethylenic polymer having a low-molecular weight obtainable by hydrogenating the macromonomer. The branched ethylenic macromonomer of the present invention is derivable from ethylene singly or derivable from ethylene and another olefin, (a) a molar ratio of a terminal methyl group/a vinyl group in the macromonomer being in the range of 1 to 100, the macromonomer having a branch other than the branch directly derived from the other olefin, (b) a ratio of vinyl groups to the total unsaturated groups in the macromonomer being 70 mol % or more, (c) a weight-average molecular weight of the macromonomer in terms of a polyethylene measured by a GPC being in the range of 100 to 20,000.

This application is a division of application Ser. No. 08/632,475 filedon Apr. 26, 1996, now U.S. Pat. No. 5,955,554 which was filed as anInternational Application PCT/JP94/01792 on Oct. 26, 1994.

DESCRIPTION

1. Technical Field

The present invention relates to a novel branched ethylenicmacromonomer, its polymer, and a branched ethylenic polymer obtainableby hydrogenating the macromonomer. More specifically, the presentinvention relates to a branched ethylenic macromonomer which canfunction as a comonomer to provide a copolymer having excellent moldingand working properties and which can be hydrogenated to provide ahydrogenated product as a wax useful in various uses, a copolymer havingthe excellent molding and working properties obtainable by using thismacromonomer as a comonomer, and a branched ethylenic polymer (a wax)having a low-molecular weight obtainable by hydrogenating themacromonomer.

2. Background Art

Heretofore, with regard to a polyethylene or an ethylene-α-olefincopolymer, its primary structure has been controlled by adjustingmolecular weight, a molecular weight distribution or copolymerizationproperties (random properties, a blocking tendency and a branchingdegree distribution), or by adding a third component such as a diene tothe polymer so as to introduce branches thereto.

On the other hand, for ethylenic polymers, various molding methods areusable, and typical known examples of the molding methods includeinjection molding, extrusion, blow molding, inflation, compressionmolding and vacuum forming. In such molding methods, the impartment ofhigh-speed molding properties and the reduction of molding energy havebeen investigated for a long period of time in order to improve workingproperties and to thus lower a working cost, and so it is an importanttheme that optimum physical properties suitable for each use is impartedand the molding can be carried out with the optimum working properties.

In recent years, it has been elucidated that a uniform metallocenecatalyst is excellent in the copolymerization properties betweenolefins, can obtain a polymer is having a narrow molecular weightdistribution, and has a much higher catalytic activity as compared witha conventional vanadium catalyst. Therefore, it has been expected thatthe metallocene catalyst will be developed in various technical fieldsby the utilization of such characteristics. However, a polyolefinobtained by the use of the metallocene catalyst is poor in molding andworking properties, and for this reason, the application of themetallocene catalyst to the blow molding and the inflation isunavoidably limited.

In order to solve such a problem, various olefinic polymers have beendisclosed into which the long-chain branches are introduced. Forexample, there have been disclosed (1) an olefin copolymer having thelong-chain branches obtained by the use of an α,ω-diene or a cyclicendomethylenic diene (Japanese Patent Application Laid-open No.34981/1972), (2) a process for preparing a copolymer containing a highernon-conjugated diene content in a high-molecular weight segment than ina low-molecular weight segment which comprises carrying outpolymerization in two steps to copolymerize the non-conjugated dienewith an olefin (Japanese Patent Application Laid-open No. 56412/1984),(3) an ethylene-α-olefin-1,5-hexadiene copolymer obtained by the use ofa metallocene/aluminoxane catalyst (Japanese Patent ApplicationPCT-through Laid-open No. 501555/1989), (4) a process for introducingthe long-chain branches by copolymerizing an α,ω-diene and ethylene inthe presence of a catalyst comprising a zero-valent or a divalent nickelcompound and a specific aminobis(imino) compound (Japanese PatentApplication Laid-open No. 261809/1990), and (5) a polyethylenecontaining both of the short-chain branches and the long-chain brancheswhich can be obtained by polymerizing ethylene alone by the use of thesame catalytic component as in the above-mentioned (4) (Japanese PatentApplication Laid-open No. 277610/1991).

However, in the copolymer of the above-mentioned (1), a crosslinkingreaction takes place simultaneously with the formation of the long-chainbranches by the diene component, and at the time of the formation of afilm, a gel is generated. In addition, melt properties inverselydeteriorate, and a control range is extremely narrow. Moreover, there isa problem that copolymerization reactivity is low, so that low-molecularweight polymers are produced, which leads to the deterioration ofphysical properties inconveniently. In the preparation process of thecopolymer described in the aforesaid (2), the long-chain branches areintroduced into the high-molecular weight component, so that themolecular weight noticeably increases due to crosslinking, and thusinsolubilization, nonfusion or gelation might inconveniently occur.Furthermore, the control range is narrow, and the copolymerizationreactivity is also low, and hence, there is a problem that owing to theproduction of the low-molecular weight polymers, the physical propertiesdeteriorate inconveniently. In the copolymer of the above-mentioned (3),a molecular weight distribution is narrow, and for this reason, thecopolymer is unsuitable for extrusion, blow molding and film formation.In addition, since branch points are formed by the progress of thecyclizing reaction of 1,5-hexadiene, an effective monomer concentrationis inconveniently low. In the process for introducing the long-chainbranches described in the above-mentioned (4), there is a problem that arange for controlling the generation of a gel and the physicalproperties is limited. In addition, the polyethylene of theabove-mentioned (5) is a polymer which contains neither ethyl branchesnor butyl branches and therefore the control of the physical properties,for example, the control of density is accomplished by methyl branches,so that the physical properties of the polyethylene tend to deteriorate.

Furthermore, there has been disclosed a method for preparing anethylenic polymer to which working properties are imparted by theutilization of copolymerization, for example, a method which comprisesforming a polymer ([η]=10-20 dl/g) by preliminary polymerization, andthen preparing an ethylene-α-olefin copolymer by main polymerization(Japanese Patent Application Laid-open No. 55410/1992). This method hasan effect that melt tension can be increased by changing the meltproperties of the obtained copolymer, but it has a drawback that a filmgel tends to occur.

In addition, there have been disclosed ethylenic polymers obtained inthe presence of a metallocene catalyst and methods for preparing thesame, for example, (1) a method for preparing an ethylenic polymer inthe presence of a constrained geometrical catalyst and an ethyleniccopolymer obtained by this method (Japanese Patent Application Laid-openNo. 163088/1991 and WO93/08221), (2) a method for preparing a polyolefinin the presence of a metallocene catalyst containing a porous inorganicoxide (an aluminum compound) as a carrier (Japanese Patent ApplicationLaid-open No. 100808/1992), and (3) an ethylene-α-olefin copolymer whichcan be derived from ethylene and the α-olefin in the presence of aspecific hafnium catalyst and which has a narrow molecular weightdistribution and improved melt flow properties (Japanese PatentApplication Laid-open No. 276807/1990).

However, in the technique of the above-mentioned (1), the obtainedethylenic copolymer has a narrow molecular weight distribution and anarrow branching degree distribution, and both of these disadvantagescannot separately be controlled. Furthermore, there is a descriptionthat in this ethylenic copolymer, long-chain branches are present and sothe ethylenic copolymer is excellent in working properties, i.e., meltflow properties, but these properties are still poor. In addition, thereis no concrete description regarding other important working properties,above all, molding stabilities (a swell ratio, melt tension and thelike).

According to the preparation method of the above-mentioned (2), theobtained copolymer of ethylene and the α-olefin has a large die swellratio, but in view of the relation of the die swell ratio to the meltingpoint of the ethylene-1-butene copolymer, it is apparent that the dieswell ratio deteriorates with the rise of the melting point. Therefore,any copolymer cannot be provided in which the die swell ratio regardinga neck-in which is a trouble at the time of the formation of a film or asheet is controllable in a wide melting point range.

On the other hand, the copolymer disclosed in the above-mentioned (3)contains an α-olefin unit as an essential unit, and it does not coverany copolymer having a resin density of more than 0.92 g/cm³.Furthermore, as in the above-mentioned (1), the obtained copolymer has anarrow molecular weight distribution and a narrow branching degreedistribution, and both of these disadvantages cannot separately becontrolled.

Moreover, WO94/07930 has disclosed a branched polyolefin having astraight-chain macromonomer segment as a branched component. In thistechnique, it has been clearly described that the activation energy ofthe melt flow and the melt tension increase as the effect of thelong-chain branch, but there is neither any description regarding theswell ratio which is extremely important as the factor of the moldingstability nor any description of a composition distribution which has alarge influence on the physical properties of the polymer. In theanalytical results of the macromonomers shown in examples, anydescription regarding an extremely important terminal unsaturated groupis not present. Therefore, it is very indefinite whether or not themacromonomer is introduced into the polymer chain by thecopolymerization.

On the other hand, a low-density polyethylene (LDPE) is most excellentin the working properties among presently existing polyethylenic resins,but its molecular structure is intricate and it has not all beenelucidated so far. Nevertheless, it is apparent that the characteristicsof the LDPE are attributed to the long-chain branch and its structure.Therefore, in order to control the swell ratio for the acquisition ofthe molding stability, such a mere introduction of the straightlong-chain branch as disclosed in WO94/07930 is insufficient.

In the ethylenic copolymer obtained by the use of the metallocenecatalyst, the molecular weight distribution is narrow and thus thebranching degree distribution is also narrow as described above, so thathighly branched low-molecular weight moieties are small and hence theimprovement of heat-sealing properties and ESCR (environmental stresscracking resistance) can be expected. Furthermore, mechanical propertiessuch as film impact can also be improved, but tearing strength inverselydeteriorates. In addition, the ethylenic copolymer has a highuniformity, and for this reason, the transparency of the film isconsidered to be excellent.

On the other hand, the ethylenic copolymer obtained by the use of aconventional heterogeneous catalyst has a wide molecular weightdistribution and a wide branching degree distribution. Particularly inthe ethylenic copolymer, the highly branched low-molecular weightmoieties are formed as by-products, and therefore the heat-sealingproperties and ESCR tend to deteriorate, but the ethylenic copolymer hasan advantage that the tearing strength is excellent.

As described above, the molecular weight distribution, the branchingdegree distribution, the long-chain branch and the structure have anextremely large influence on a resin performance, and the ethyleniccopolymers in which these factors have optionally be controlled cansuitably be used in various application fields.

On the other hand, when the branched ethylenic macromonomer is used as acomonomer, the long-chain branch can easily be introduced into theobtained copolymer without gelation, and as a result, the copolymer canpossess the excellent molding and working properties. Furthermore, whenthe branched ethylenic macromonomer is hydrogenated, the branchedethylenic polymer having a low molecular weight can be obtained whichare useful as a wax in various uses such as a base oil for a lubricatingoil and an additive having a controlled viscosity index.

As understood from the foregoing, the branched ethylenic macromonomer isan extremely useful compound.

As a method for preparing a low-molecular weight polyethylene (apolyethylene wax), there has been disclosed a method which comprises thegaseous phase polymerization of ethylene in the presence of hydrogen bythe use of a metallocene catalyst (Japanese Patent ApplicationPCT-through Laid-open No. 502209/1991). In this method, however,hydrogen is used for the adjustment of the molecular weight, andtherefore the content of a terminal vinyl group unavoidably deteriorates(in an α-olefin/ethylene copolymer system, it further deteriorates). Inconsequence, the thus obtained low-molecular weight polyethylene cannotbe used as the macromonomer.

Furthermore, there has also been disclosed a method for polymerizingethylene in the presence of a Ti(OR)₄ (R is an alkyl group or an arylgroup) catalyst (Japanese Patent Application Laid-open No. 61932/1987).However, this method intends to prepare 1-butene, which is a dimer ofethylene, in a high yield, and in this case, the dimer and the trimer ofethylene as well as an ethylene/1-butene copolymer can be produced, butan ethylene oligomer which is useful as the macromonomer cannot beproduced.

DISCLOSURE OF THE INVENTION

The present invention has been developed under such circumstances, andan object of the present invention is to provide a novel branchedethylenic macromonomer which can function as a comonomer to produce acopolymer having excellent molding and working properties and which canbe hydrogenated to produce a branched ethylenic polymer having a lowmolecular weight as a wax useful in various uses, a copolymer having theexcellent molding and working properties obtainable by using thismacromonomer as a comonomer, and a branched ethylenic polymer having alow-molecular weight obtained by hydrogenating the macromonomer.

The present inventors have intensively researched to achieve theabove-mentioned object, and as a result, it has been found that abranched ethylenic macromonomer which is derived from ethylene alone orfrom ethylene and one or more of an α-olefin, an cyclic olefin and astyrene and in which a molar ratio between a terminal methyl group and avinyl group is within a specific range and which has a branch other thanthe branch directly derived from the α-olefin, the cyclic olefin and thestyrene and which a ratio of vinyl groups to the total unsaturatedgroups and a weight-average molecular weight are within specific rangescan function as a comonomer to produce a copolymer having excellentmolding and working properties, and a copolymer which can be obtained bycopolymerizing the macromonomer with one or more of ethylene, theα-olefin, the cyclic olefin and the styrene and which containsmacromonomer segments in a specific ratio and which has an intrinsicviscosity within a specific range is excellent in the molding andworking properties. In addition, it has also been found that a branchedethylenic polymer having a low molecular weight which can be obtained byhydrogenating the branched ethylenic macromonomer and which does notsubstantially contain an unsaturated group is useful as a wax in varioususes. The present invention has been completed on the basis of suchknowledges.

That is to say, the present invention is directed to

(1) a branched ethylenic macromonomer which is derivable from ethyleneor derivable from ethylene and at least one selected from the groupconsisting of α-olefins having 3 to 20 carbon atoms, cyclic olefins andstyrenes, (a) a molar ratio of a terminal methyl group to a vinyl group[the terminal methyl group/the vinyl group] in the macromonomer being inthe range of 1 to 100, the macromonomer having a branch other than thebranch directly derived from the α-olefin, the cyclic olefin or thestyrene, (b) a ratio of vinyl groups to the total unsaturated groups inthe macromonomer being 70 mol% or more, (c) a weight-average molecularweight (Mw) of the macromonomer in terms of a polyethylene measured by agel permeation chromatography being in the range of 100 to 20,000,

(2) a copolymer which is derivable from a branched ethylenicmacromonomer described in the above-mentioned (1) and at least oneselected from the group consisting of ethylene, α-olefins having 3 to 20carbon atoms, cyclic olefins and styrenes, the content of a macromonomersegment in the copolymer being in the range of 0.001 to 90% by weight,an intrinsic viscosity of the copolymer measured in decalin at atemperature of 135° C. being in the range of 0.01 to 20 dl/g, and

(3) a branched ethylenic polymer not substantially containing anunsaturated group which is obtainable by hydrogenating a branchedethylenic macromonomer described in the above-mentioned (1).

BEST MODE FOR CARRYING OUT THE INVENTION

A branched ethylenic macromonomer of the present invention can bederived from ethylene singly or derived from ethylene and at least oneselected from the group consisting of α-olefins having 3 to 20 carbonatoms, cyclic olefins and styrenes. Here, examples of the α-olefinshaving 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene,1-octene, 1-decene, 1-eicosene, 4-methyl-1-pentene, 1-tetradecene and3-methyl-1-butene. Examples of the cyclic olefins include norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene,5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene,1,4,5,8-dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-methyl-1,4,5,8-dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethanol-1,2,3,4,4a,5,8, 8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyliden-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-cyclohexyl-1,4,5,8-dimethano1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,2-dihydrodicyclopentadiene, 5-chloronorbornene,5,5-dichloronorbornene, 5-fluoronorbornene,5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene,5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydride,5-dimethylaminonorbornene and 5-cyananorbornene.

Examples of the styrenes include styrene, alkylstyrenes such asp-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene,2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene andp-tert-butylstyrene, halogenated styrenes such as p-chlorostyrene,m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene ando-methyl-p-fluorostyrene, vinylbiphenyls such as 4-vinylbiphenyl,3-vinylbiphenyl and 2-vinylbiphenyl, and vinylphenylnaphthalenes such as1-(4-vinylphenyl)-naphthalene, 2-(4-vinylphenyl)-naphthalene,1-(3-vinylphenyl)-naphthalene, 2-(3-vinylphenyl)-naphthalene,1-(2-vinylphenyl)-naphthalene and 2-(2-vinylphenyl)-naphthalene.

These monomers which can be copolymerized with ethylene may be usedsingly or in a combination of two or more thereof.

In the branched ethylenic macromonomer of the present invention, a molarratio of a terminal methyl group to a vinyl group [the terminal methylgroup/the vinyl group] is in the range of 1 to 100, and the macromonomeris required to have a branch. A copolymerized macromonomer has a branchother than the branch directly derived from the α-olefin, the cyclicolefin or the styrene. The branch present in this macromonomer is ashort-chain branch whose main chain has 1 to 5 carbon atoms, such as amethyl branch, an ethyl branch, a propyl branch or a butyl branch, or along-chain branch whose main chain has 6 or more carbon atoms, such as ahexyl branch or a branch having carbon atoms more than the hexyl branch.Two or more of these branches may be present in the macromonomer. Thechain length of the branch preferably is 4 or more, more preferably 6 ormore in terms of the number of carbon atoms. If the carbon atoms of thebranch are less than 4, the various characteristics of the branchedmacromonomer, for example, the effect of imparting a sufficient moldingstability to the copolymer of ethylene is poor. This branch may containan α-olefin other than ethylene, a cyclic olefin or a styrene. Theidentification of the branch present in the macromonomer can be carriedout in a usual manner by the use of ¹³C-NMR, when the branch has 4 orless carbon atoms. On the other hand, with regard to the long-chainbranch having 6 or more carbon atoms, its presence can be confirmed by¹³C-NMR, but its chain length cannot be determined. As effective meansof the determination, there are an analysis of a molten fluid and ananalysis of a macromonomer solution. According to these analyticalmeans, the presence of the long-chain branch can be confirmed, and adifference between structures of the branched macromonomer and astraight-chain macromonomer can also be elucidated.

The vinyl group and the methyl branch can be determined by ¹H-NMR(nuclear magnetic resonance spectrum) and the measurement of ¹³C-NMR[CDCl₃, 50° C. or TCB/C₆D₆ (80/20 v/v), measured at 130° C.].

That is to say, in the measurement of ¹H-NMR, peaks attributed to thevinyl group are present at 4.8-5.0 ppm and 5.6-5.8 ppm, and an intensityratio of the peak of the methyl group at 0.7-0.9 ppm to the peak of thevinyl group at 4.8-5.0 ppm is usually

1.0<(0.7-0.9 ppm)/(4.8-5.0 ppm)≦150

preferably

1.5<(0.7-0.9 ppm)/(4.8-5.0 ppm)≦100.

Furthermore, in the measurement of ¹³C-NMR, the ethyl branch bonded to aquaternary carbon which is observed in LDPE (low-density polyethylene)is not present (the methyl group: 8 ppm).

In the branched ethylenic macromonomer, a ratio of the vinyl groups tothe total unsaturated groups is required to be 70 mol % or more,preferably 75 mol % or more, more preferably 80 mol % or more. If thisratio is less than 70 mol %, the copolymerization efficiency of themacromonomer deteriorates.

Furthermore, with regard to the branched ethylenic macromonomer, itsweight-average molecular weight (Mw) in terms of a polyethylene measuredby a gel permeation chromatography is required to be in the range of 100to 20,000, preferably 150 to 18,000, more preferably 180 to 16,000.

On the other hand, the copolymer of the present invention can be derivedfrom the branched ethylenic macromonomer and at least one selected fromthe group consisting of ethylene, α-olefins having 3 to 20 carbon atoms,cyclic olefins and styrenes. Examples of the α-olefins having 3 to 20carbon atoms, the cyclic olefins and the styrenes include thoseenumerated in the aforesaid description of the branched ethylenicmacromonomer. These monomers which can be copolymerized with thebranched ethylenic macromonomer can be used singly or in a combinationof two or more thereof.

In the copolymer of the present invention, the content of a branchedethylenic macromonomer segment is required to be in the range of 0.001to 90% by weight, preferably 0.002 to 85% by weight, more preferably0.01 to 80% by weight. If the content of the macromonomer segment isless than 0.001% by weight, the copolymer is poor in non-Newtonianproperties and melt tension, so that the improvement effect of themolding and working properties cannot sufficiently be exerted. If it ismore than 90% by weight, the mechanical strength of the copolymerdeteriorates.

The content of the macromonomer segment can be calculated from adifference between the yield of the polymer and the amount of thereacted olefin obtained by subtracting the amount of the unreactedolefin from that of the fed olefin. Furthermore, in the case of theethylene/macromonomer system, the content of the macromonomer segmentcan also be calculated from a molar ratio between a main chain methylenegroup and a methyl group based on the macromonomer segment. In thiscase, the molar ratio between the methylene group and the methyl group[the methylene group/the methyl group] is usually in the range of 1.5 to3000.

In the copolymer of the present invention, it is preferred that theweight-average molecular weight (Mw) and a die swell ratio (D_(R)) meetthe equation

D _(R)>0.5+0.125×logMw,

preferably

1.80>DR>0.36+0.159×logMw,

more preferably

1.75>DR>0.16+0.210×logMw,

most preferably

1.70>DR>−0.11+0.279×logMw.

If DR is not more than [0.5+0.125×logMw], the sufficient swell cannot beobtained, and a problem such as a neck-in takes place at the time ofextrusion.

Here, the die swell ratio (D_(R)) is a value (D₁/D₀) obtained bymeasuring a diameter (D₁, mm) of a strand formed by extrusion through acapillary nozzle [diameter (D₀)=1.275 mm, length (L)=51.03 mm, L/D₀=40,and entrance angle=90°] at an extrusion speed of 1.5 mm/min (shearrate=10 sec⁻¹) at a temperature of 190° C. by the use of a capillographmade by Toyo Seiki Seisakusho Co., Ltd., and then dividing this diameterby the diameter of the capillary nozzle.

The above-mentioned diameter (D₁) of the strand is an average value ofvalues obtained by measuring long axes and short axes of centralportions of 5 samples having a extruded strand length of 5 cm (a lengthof 5 cm from a nozzle outlet).

Moreover, in the copolymer, it is suitable that a relation between ahalf value width [W (°C.)] of the main peak of a compositiondistribution curve obtained by a temperature rising elutionfractionation method and the temperature position [T (°C.)] of a mainpeak top meets the equation

W≧−24.9+2470/T

preferably

W≧−23.9+2470/T

more preferably

W≧−21.9+2470/T

much more preferably

W≧−20.0+2470/T

most preferably

W≧−18.0+2470/T.

If this W is less than [−24.9+2470/T], the copolymer is unpreferablypoor in melt physical properties and mechanical properties.

The above-mentioned W and T are values obtained by the followingtemperature rising elution fractionation method. That is to say, apolymer solution of o-dichlorobenzene whose concentration is adjusted toabout 6 g/liter at 135° C. is injected, by a constant delivery pump,into a column having an inner diameter of 10 mm and a length of 250 mmwhich is filled with Chromosorb PNAN (80/100 mesh) as a column filler.The polymer solution is cooled to room temperature at a rate of 10°C./hr, so that the polymer is adsorbed and crystallized on the filler.Afterward, o-dichlorobenzene is fed at a feed rate of 2 cc/min underheat-up rate conditions of 20° C./hr. Then, the concentration of theeluted polymer is measured by an infrared detector (device: 1-A Fox BoroCVF Co., Ltd., cell: CaF₂), and the composition distribution curve to anelution temperature is depicted to obtain W and T.

The copolymer of the present invention may be any of a random copolymer,a block copolymer and a graft copolymer, and in the case that theα-olefin having 3 to 20 carbon atoms is used, the copolymer may containany stricture of an atactic structure, an isotactic structure and asyndiotactic structure. An intrinsic viscosity of the copolymer measuredin decalin at a temperature of 135° C. is required to be in the range of0.01 to 20 dl/g, preferably 0.05 to 18 dl/g, more preferably 0.1 to 15dl/g. If this intrinsic viscosity is less than 0.01 dl/g, the copolymeris poor in mechanical properties, and if it is more than 20 dl/g, itsmolding and working properties deteriorate. In addition, a ratio Mw/Mnof a weight-average molecular weight (Mw) to a number-average molecularweight (Mn) of the copolymer in terms of a polyethylene measured by agel permeation chromatography is usually in the range of 1.5 to 70.

The branched ethylenic macromonomer of the present invention can beprepared by polymerizing ethylene singly or polymerizing ethylene and atleast one selected from the group consisting of α-olefins having 3 to 20carbon atoms, cyclic olefins and styrenes in the presence of apolymerization catalyst which permits the production of the macromonomerhaving the above-mentioned characteristics. Furthermore, the copolymerof the present invention can be prepared by copolymerizing the branchedethylenic macromonomer and at least one selected from the groupconsisting of ethylene, α-olefins having 3 to 20 carbon atoms, cyclicolefins and styrenes in the presence of a polymerization catalyst.

An example of the polymerization catalyst which can be used in thepreparation of the branched ethylenic macromonomer and the copolymercontains, as main components, (A) a transition metal compound and (B) acompound capable of forming an ionic complex from the transition metalcompound or its derivative.

As the transition metal compound of the component (A) in the catalyst,there can be used a transition metal compound containing a metal in thegroups 3 to 10 of the periodic table or a metal of a lanthanide series.Examples of such a transition metal compound includes various kinds ofcompounds, and compounds containing transition metals in the groups 4, 5and 6 can be suitably used. Particularly suitable are compoundsrepresented by the general formulae

CpM¹R¹ _(a)R² _(b)R³ _(c)  (I)

Cp₂M¹R¹ _(a)R² _(b)  (II)

(Cp-A_(e)-Cp)M¹R¹ _(a)R² _(b)  (III)

or the general formula

M¹R¹ _(a)R² _(b)R³ _(c)R⁴ _(d)  (IV)

and their derivatives.

In the above-mentioned general formulae (I) to (IV), M¹ represents atransition metal such as titanium, zirconium, hafnium, vanadium, niobiumand chromium, and Cp represents a cyclic unsaturated hydrocarbon groupor a chain unsaturated hydrocarbon group such as a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a tetrahydroindenyl group, a substitutedtetrahydroindenyl group, a fluorenyl group or a substituted fluorenylgroup. R¹, R², R³ and R⁴ each independently represents a σ-bond ligand,a chelate ligand or a ligand such as a Lewis base, and typical examplesof the a-bond ligand include a hydrogen atom, an oxygen atom, a halogenatom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkylgroup having 6 to 20 carbon atoms, an acyloxy group having 1 to 20carbon atoms, an allyl group, a substituted allyl group, and asubstituent containing a silicon atom. In addition, examples of thechelate ligand include an acetylacetonato group and a substitutedacetylacetonato group. A represents a crosslinkage by a covalent bond.a, b, c and d each is independently an integer of 0 to 4, and e is aninteger of 0 to 6. Two or more of R¹, R², R³ and R⁴ may bond to eachother to form a ring. In the case that the above-mentioned Cp has asubstituent, this substituent is preferably an alkyl group having 1 to20 carbon atoms. In the formulae (II) and (III), the two Cps may be thesame or different from each other.

Examples of the substituted cyclopentadienyl group in theabove-mentioned formulae (I) to (III) include a methylcyclopentadienylgroup, an ethylcyclopentadienyl group, an isopropylcyclopentadienylgroup, a 1,2-dimethylcyclopentadienyl group, atetramethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group,a 1,2,3-trimethylcyclopentadienyl group, a1,2,4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienylgroup and a trimethylsilylcyclopentadienyl group. Furthermore, typicalexamples of R¹ to R⁴ in the above-mentioned formulae (I) to (IV) includea fluorine atom, a chlorine atom, a bromine atom and an iodine atom asthe halogen atoms; a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an octyl group and a 2-ethylhexylgroup as the alkyl groups having 1 to 20 carbon atoms; a methoxy group,an ethoxy group, a propoxy group, a butoxy group and a phenoxy group asthe alkoxy groups having 1 to 20 carbon atoms; a phenyl group, a tolylgroup, a xylyl group and a benzyl group as the aryl groups, thealkylaryl groups or the arylalkyl groups having 6 to 20 carbon atoms; aheptadecylcarbonyloxy group as the acyloxy group having 1 to 20 carbonatoms; a trimethylsilyl group and a (trimethylsilyl)methyl group as thesubstituent containing a silicon atom; and ethers such as dimethylether, diethyl ether and tetrahydrofuran, a thioether such astetrahydrothiophene, an ester such as ethyl benzoate, nitrites such asacetonitrile and benzonitrile, amines such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline, pyridine,2,2′-bipyridine and phenanthroline, phosphines such as triethylphosphineand triphenylphosphine, chain unsaturated hydrocarbons such as ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and theirderivatives, and cyclic unsaturated hydrocarbons such as benzene,toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene,cyclooctatetraene and their derivatives as the Lewis base. In addition,examples of the crosslinkage by the covalent bond of A in the formula(III) include a methylene crosslinkage, a dimethylmethylenecrosslinkage, an ethylene crosslinkage, a 1,1′-cyclohexylenecrosslinkage, a dimethylsilylene crosslinkage, a dimethylgermilenecrosslinkage and a dimethylstanilene crosslinkage.

Examples of the compound represented by the general formula (I) include

(pentamethylcyclopentadienyl)trimethylzirconium,(pentamethylcyclopentadienyl)triphenylzirconium,(pentamethylcyclopentadienyl)tribenzylzirconium,(pentamethylcyclopentadienyl)trichlorozirconium,(pentamethylcyclopentadienyl)trimethoxyzirconium,(cyclopentadienyl)trimethyzirconium,(cyclopentadienyl)triphenylzirconium,(cyclopentadienyl)tribenzylzirconium,(cyclopentadienyl)trichlorozirconium,(cyclopentadienyl)trimethoxyzirconium,(cyclopentadienyl)dimethyl(methoxy)zirconium,(methylcyclopentadienyl)trimethylzirconium,(methylcyclopentadienyl)triphenylzirconium,(methylcyclopentadienyl)tribenzylzirconium,(methylcyclopentadienyl)trichlorozirconium,(methylcyclopentadienyl)dimethyl(methoxy)zirconium,(dimethylcyclopentadienyl)trichlorozirconium,(trimethylcyclopentadienyl)trichlorozirconium,(trimethylcyclopentadienyl)trimethylzirconium,(tetramethylcyclopentadienyl)trichlorozirconium, and these compounds inwhich zirconium is replaced with titanium or hafnium.

Examples of the compound represented by the general formulae (II)include

bis(cyclopentadienyl)dimethylzirconium,bis(cyclopentadienyl)diphenylzirconium,bis(cyclopentadienyl)diethylzirconium,bis(cyclopentadienyl)dibenzylzirconium,bis(cyclopentadienyl)dimethoxyzirconium,bis(cyclopentadienyl)dichlorozirconium,bis(cyclopentadienyl)dihydridozirconium,bis(cyclopentadienyl)monochloromonohydridozirconium,bis(methylcyclopentadienyl)dimethylzirconium,bis(methylcyclopentadienyl)dichlorozirconium,bis(methylcyclopentadienyl)dibenzylzirconium,bis(pentamethylcyclopentadienyl)dimethylzirconium,bis(pentamethylcyclopentadienyl)dichlorozirconium,bis(pentamethylcyclopentadienyl)dibenzylzirconium,bis(pentamethylcyclopentadienyl)chloromethylzirconium,bis(pentamethylcyclopentadienyl)hydridomethylzirconium,(cyclopentadienyl)(pentamethylcyclopentadienyl)dichlorozirc onium, andthese compounds in which zirconium is replaced with titanium or hafnium.

Furthermore, examples of the compound represented by the general formula(III) include

ethylenebis(indenyl)dimethylzirconium,ethylenebis(indenyl)dichlorozirconium,ethylenebis(tetrahydroindenyl)dimethylzirconium,ethylenebis(tetrahydroindenyl)dichlorozirconium,dimethylsilylenebis(cyloropentadienyl)dimethylzirconium,dimethylsilylenebis(cyloropentadienyl)dichlorozirconium,isopropylidene(cyloropentadienyl)(9-fluorenyl)dimethylzirconium,isopropylidene(cyloropentadienyl)(9-fluorenyl)dichlorozirconium,[phenyl(methyl)methylene](9-fluorenyl)(cycylopentadienyl)dimethylzirconium,diphenylmethylene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium,ethylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,cyclohexalidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,cyclopentylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,cyclobutylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,dimethylsilylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium,dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dimethylzirconium,dimethylsilylenebis(indenyl)dichlorozirconium, and these compounds inwhich zirconium is replaced with titanium or hafnium.

Moreover, examples of the compound represented by the general formula(IV) include tetramethylzirconium, tetrabenzylzirconium,tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium,tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium,dibutoxydichlorozirconium, bis(2,5-di-t-butylphenoxy)dimethylzirconium,bis(2,5-di-t-butylphenoxy)dichlorozirconium, zirconiumbis(acetylacetonato), and these compounds in which zirconium is replacedwith titanium or hafnium.

Typical examples of the vanadium compound include vanadium trichloride,vanadyl trichloride, vanadium triacetylacetonate, vanadiumtetrachloride, vanadium tributoxide, vanadyl dichloride, vanadylbisacetylacetonate, vanadyl triacetylacetonate, dibenzenevanadium,dicyclopentadienylvanadium, dicyclopentadienylvanadium dichloride,cyclopentadienylvanadium dichloride anddicyclopentadienylmethylvanadium.

Next, typical examples of the chromium compound includetetramethylchromium, tetra(t-butoxy)chromium,bis(cyclopentadienyl)chromium,hydridotricarbonyl(cyclopentadienyl)chromium,hexacarbonyl(cyclopentadienyl)chromium, bis(benzene)chromium,tricarbonyltris(triphenyl phosphonate)chromium, tris(allyl)chromium,triphenyltris(tetrahydrofuran)chromium and chromiumtris(acetylacetonate).

Furthermore, as the component (A), there can suitably be used a group 4transition compound having, as the ligand, a multiple ligand compound inwhich in the above-mentioned general formula (III), two substituted orunsubstituted conjugated cyclopentadienyl groups (however, at least oneof which is a substituted cyclopentadienyl group) is bonded to eachother via an element selected from the group 14 of the periodic table.

An example of such a compound is a compound represented by the generalformula (V)

or its derivative.

In the above-mentioned general formula (V), Y¹ represents a carbon atom,a silicon atom, a germanium atom or a tin atom, R⁵ _(t)—C₅H_(4-t) and R⁵_(u)—C₅H_(4-u) each represents a substituted cyclopentadienyl group, andt and u each are an integer of 1 to 4. Here, R⁵s each represents ahydrogen atom, a silyl group or a hydrocarbon group, and they may be thesame or different from each other. In at least either of thecyclopentadienyl groups, R⁵ is present on at least either of carbonatoms adjacent to the carbon atom bonded to Y¹. R⁶ represents a hydrogenatom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, analkylaryl group or an arylalkyl group having 6 to 20 carbon atoms. M²represents a titanium atom, a zirconium atom or a hafnium atom, X¹represents a hydrogen atom, a halogen atom, an alkyl group having 1 to20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl grouphaving 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbonatoms. X¹ may be the same or different from each other, and similarly,R⁶ is may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the generalformula (V) include a methylcyclopentadienyl group, anethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienylgroup, a 1,2,3-trimethylcyclopentadienyl group and a1,2,4-trimethylcyclopentadienyl group. Typical examples of X¹ include F,Cl, Br and I as the halogen atoms; a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, an octyl group anda 2-ethylhexyl group as the alkyl group having 1 to 20 carbon atoms; amethoxy group, an ethoxy group, a propoxy group, a butoxy group and aphenoxy group as the alkoxy groups having 1 to 20 carbon atoms; and aphenyl group, a tolyl group, a xylyl group and a benzyl group as thearyl group, the alkylaryl group or the arylalkyl group having 6 to 20carbon atoms. Typical examples of the R⁶ include a methyl group, anethyl group, a phenyl group, a tolyl group, a xylyl group and a benzylgroup.

In addition, the compound having the general formula (V) also includescompounds represented by the general formula (VI):

In the compound of the general formula (VI), Cp represents a cyclicunsaturated hydrocarbon group or a chain unsaturated hydrocarbon groupsuch as a cyclopentadienyl group, a substituted cyclopentadienyl group,an indenyl group, a substituted indenyl group, a tetrahydroindenylgroup, a substituted tetrahydroindenyl group, a fluorenyl group or asubstituted fluorenyl group. M³ represents a titanium atom, a zirconiumatom or a hafnium atom, X² represents a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylarylgroup or an arylalkyl group having 6 to 20 carbon atoms, or an alkoxygroup having 1 to 20 carbon atoms. Z represents SiR⁷ ₂, CR⁷ ₂, SiR⁷₂SiR⁷ ₂, CR⁷ ₂CR⁷ ₂, CR⁷ ₂CR⁷ ₂CR⁷ ₂, CR⁷═CR⁷, CR⁷ ₂SiR⁷ ₂ or GeR⁷ ₂,and Y² represents —N(R⁶)—, —O—, —S— or —P(R⁶)—. The above-mentioned R⁷is a group selected from the group consisting of a hydrogen atom, analkyl group having 20 or less non-hydrogen atoms, an aryl group, a silylgroup, a halogenated alkyl group, a halogenated aryl group and acombination thereof, and R⁸ is an alkyl group having 1 to 10 carbonatoms or an aryl group having 6 to 10 carbon atoms, or R8 may form acondensed ring of one or more R⁷s and 30 or less non-hydrogen atoms.Moreover, w represents 1 or 2.

Typical examples of the compound represented by the general formula (VI)include(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride,(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride, (methylamido) (tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride,(ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitaniumdichloride,(tertbutylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride,(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl,(benzylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride and(phenylphosphide)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl.

Furthermore, as the transition metal compound which is the component(A), there can also be used a reaction product of a transition metalcompound represented by the general formula (IV) in which at least twohalogen atoms, an alkoxy group, or the two halogen atoms and the alkoxygroup are bonded to a central metal and any one of diols represented bythe general formulae (VII) to (XII):

In the compounds represented by the general formulae (VII) to (XII), R⁹and R¹⁰ are each a hydrocarbon group having 1 to 20 carbon atoms, andthey may be the same of different from each other, Y³ is a hydrocarbongroup having 1 to 20 carbon atoms, or a group represented by

wherein R¹⁵ is a hydrocarbon group having 1 to 6 carbon atoms. Examplesof the hydrocarbon group having 1 to 20 carbon atoms which isrepresented by R⁹, R¹⁰ and y³ include methylene, ethylene, trimethylene,propylene, diphenylmethylene, ethylidene, n-propylidene, isopropylidene,n-butylidene and isobutylidene, and above all, methylene, ethylene,ethylidene, isopropylidene and isobutylidene are preferable. n is aninteger of 0 or more, and 0 or 1 is particularly preferable.

Furthermore, R¹¹, R¹², R¹³ and R¹⁴ are each a hydrocarbon group having 1to 20 carbon atoms, a hydroxyl group, a nitro group, a nitrile group, ahydrocarbyloxy group or a halogen atom, and they may be the same ordifferent from each other. Examples of the hydrocarbon group having 1 to20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl,n-heptyl, n-octyl, n-decyl and n-dodecyl; aryl groups such as phenyl andnaphthyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; analkenyl group such as propenyl; and an aralkyl group such as benzyl, andabove all, the alkyl groups having 1 to 10 carbon atoms are preferable.y, y′, y″, y′″, z, z′, z″ and z′″ are each the number of substituentsbonded to an aromatic ring, and y, y′, z and z′ are each an integer of 0to 4, y″ and z″ are each an integer of 0 to 2, and y′″ and z′″ are eachan integer of 0 to 3.

One example of the reaction product of the transition metal compound andeach of the diols represented by the general formulae (VII) to (XII) isa compound represented by the general formula (XIII):

In the general formula (XIII), M¹ is as defined above, E¹ and E² areeach a hydrocarbon group having 1 to 20 carbon atoms, v and x are each 0or 1, and E¹ and E² form a crosslinking structure via y⁴. E³ and E⁴ areeach a σ-bond ligand, a chelate ligand or a Lewis base, and they may bethe same or different from each other.

v′ and x′ are each an integer of 0 to 2 [v′+x′=an integer of (thevalence of M¹−2)]. y⁴ is a hydrocarbon group having 1 to 20 carbonatoms, E⁵E⁶Y⁵, an oxygen atom or a sulfur atom, and m is an integer of 0to 4. E⁵ and E⁶ are each a hydrocarbon group having 1 to 20 carbonatoms, and Y⁵ is a carbon atom or a silicon atom.

In the preparation of the branched ethylenic macromonomer, theparticularly preferable transition metal compound is an alkoxy compoundof titanium.

Furthermore, as the transition metal compound of the component (A),there can be used a multiple crosslinking type compound having astructure represented by the general formula (XIV):

In the above-mentioned general formula (XIV), M is a metallic element inthe groups 3 to 10 or a lanthanoide series of the periodic table, andtypical examples of M include titanium, zirconium, hafnium, yttrium,vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanoidemetals. Above all, titanium, zirconium and hafnium are preferable fromthe viewpoint of an olefin polymerization activity. E⁷ and E⁸ are each aσ-bonding or a π-bonding ligand, and they form a crosslinking structurevia (A¹)_(p), (A²)_(p), . . . (A^(n))_(p) and (D)_(s) and may be thesame or different. Typical examples of E⁷ include a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amido group (—N<), a phosphide group(—P<), a hydrocarbon group (>CR— or >C<), a silicon-containing group(>SiR— or >Si<) (wherein R is hydrogen, a hydrocarbon group having 1 to20 carbon atoms, or a hetero-atom-containing group). Typical examples ofE⁸ include a cyclopentadienyl group, a substituted cyclopentadienylgroup, an indenyl group, a substituted indenyl group, aheterocyclopentadienyl group, a substituted heterocyclopentadienylgroup, an amido group (—N< or —NR—), a phosphide group (—P< or —PR—),oxygen (—O—), sulfur (—S—), selenium (—Se—), a hydrocarbon group(>C(R)₂—, >CR— or >>C<), a silicon-containing group (>SiR—, >Si(R)₂—or >Si<) (wherein R is hydrogen, a hydrocarbon group having 1 to :?0carbon atoms, or a hetero-atom-containing group).

Furthermore, X is a σ-bonding ligand, and when a plurality of Xs arepresent, these plural Xs may be the same or different, and each X maycrosslink with another X, E⁷, E⁸ or Y. Typical examples of X include ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, an aryloxy group having 6 to 20carbon atoms, an amido group having 1 to 20 carbon atoms, asilicon-containing group having 1 to 20 carbon atoms, a phosphide grouphaving 1 to 20 carbon atoms, a sulfide group having I to 20 carbon atomsand an acyl group having 1 to 20 carbon atoms. On the other hand, Y is aLewis base, and when a plurality of Ys are present, these plural Ys maybe the same or different, and each Y may crosslink with another Y, E⁷,E⁸ or X. Typical examples of the Lewis base which is represented by Yinclude an amine, an ether, a phosphine and a thioether.

Next, A¹, A², An are each a crosslinking group and they may be the sameor different. Typical examples of this crosslinking group include groupshaving a structure in which the crosslinking is made with one carbonatom, such as methylene, ethylene, ethylidene, isopropylidene,cyclohexylidene, 1,2-cyclohexylene and vinylidene (CH₂═C═).

Other typical structures of A¹, A², . . . A^(n) include R′₂Si, R′₂Ge,R′₂Sn, R′Al, R′P, R′P (═O), R′N, oxygen (—O—), sulfur (—S—) and selenium(—Se—) wherein R′ is a hydrogen atom, a halogen atom, a hydrocarbongroup having 1 to 20 carbon atoms, a halogen-containing hydrocarbongroup having 1 to 20 carbon atoms, a silicon-containing group or ahetero-atom-containing group, and when two Rs are present, they may bethe same or different and may bond to each other to form a ringstructure. Typical examples of these crosslinking groups includedimethylsilylene, tetramethyldisilylene, dimethylgermylene,dimethylstannylene, methylborilidene (CH₃—B<), methylalumilidene(CH₃—Al<), phenylphosphilidene (Ph—P<), phenylphospholidene

methylimide, oxygen (—O—), sulfur (—S—) and selenium (—Se—). Inaddition, examples of A¹, A², . . . A^(n) include vinylene (—CH═CH—),o-xylylene

and 1,2-phenylene.

D represents a crosslinking group, and when a plurality of Ds arepresent, these plural Ds may be the same or different. Typical examplesof D include R″C, R″Si, R″Ge, R″Sn, B, Al, P, P(═O) and N wherein R″ isa hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20carbon atoms, a halogen-containing hydrocarbon group having 1 to 20carbon atoms, a silicon-containing group or a hetero-atom-containinggroup. Furthermore, n is an integer of 2 to 4; p is an integer of 1 to4, and the respective ps may be the same or different; q is an integerof 1 to 5 [(the valence of M)−2]; r is an integer of 0 to 3; and s is aninteger of 0 to 4, and when s is 0, (A¹)_(p), (A²)_(p), . . .(A^(n))_(p) and E² form a direct bond.

Of the compounds represented by the above-mentioned general formula(XIV), a transition metal compound represented by the following generalformula (XV) is preferable in which s is 0, i.e., any crosslinking groupof D is not present:

wherein M, E⁷, E⁸, X, Y, A¹, A², . . . A^(n), n, p, q and r are asdefined above.

Typical examples of such a transition metal compound include(1,1′-dimethylsilylene)(2,2′-isopropylidene)bis(cyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-dimethylsilylene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdimethyl,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdibenzyl,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumbis(trimethylsilyl),(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumbis(trimethylsilylmethyl),(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdimethoxide,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumbis(trifluoromethanesulfonate),(1,1′-dimethylsilylene)(2,2′-methylene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-methylene)-bis(cyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-ethylene)-bis-(indenyl)zirconiumdichloride, (1,1′-dimethylsilylene)(2,2′-ethylene)-bis(indenyl)zirconiumdichloride,(1,1′-ethylene)-(2,2′-dimethylsilylene)-bis(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-cyclohexylidene)-bis(indenyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-dimethylsilylene)-bis(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdimethyl,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdibenzyl,(1,1′-dimethylsilylene)(2,2′-isopropylidene)bis(indenyl)zirconiumbis(trimethylsilyl),(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumbis(trimethylsilylmethyl),(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdimethoxide,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumbis(trifluoromethanesulfonate),(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1′-isopropylidene)(2,2′-ethylene)-bis(indenyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3,4-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(4-methylcyclopentadienyl)(4′-methylcyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)(3,4,5-trimethylcyclopentadienyl)(3′,4′,5′-trimethylcyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(4-n-butylcyclopentadienyl)(4′-n-butylcyclopentadienyl)zirconiumdichloride, (1,1-dimethylsilylene)(2,2′-isopropylidene)(4-tert-butylcyclopentadienyl)(4′-tert-butylcyclopentadienyl)zirconiumdichloride,(1,2′-dimethylsilylene)(2,1′-isopropylidene)-(3-methylindenyl)(3′-methylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-methylindenyl)(3′-methylindenyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-dimethylsilylene)-(3-methylindenyl)(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)(4,7-dimethylindenyl)(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(4,5-benzoindenyl)(indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(4,7-dimethylindenyl)(4′,7′-dimethyl-indenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(4,5-benzoindenyl)(4,5-benzoindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-methylindenyl)(3′-methylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-ethylindenyl)(3′-ethylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-n-butylindenyl)(3′-n-butylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-tert-butylindenyl)(3′-tert-butylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-trimethylsilylindenyl)(3′-trimethylsilylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(3-benzylindenyl)(3′-benzylindenyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-ethylene)-(indenyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-dimethylsilylene)(2,2′-isopropylidene)(indenyl)(cyclopentadienyl)zirconiumdichloride, (3,3′-isopropylidene)(4,4′-isopropylidene)-(1-phosphacyclopentadienyl)(1′-phosphacyclopentadienyl)zirconiumdichloride,(3,1′-isopropylidene)(4,2′-isopropylidene)-(1-phosphacyclopentadienyl)(4′-cyclopentadienyl)zirconiumdichloride, and these compounds in which zirconium is replaced withtitanium or hafnium. Needless to say, they are not restrictive. Inaddition, similar compounds containing metallic elements in other groupsand a lanthanoide series of the periodic table are also usable.

These transition metal compounds of the component (A) may be used singlyor in a combination of two or more thereof.

On the other hand, examples of a compound which can be used as thecomponent (B) in the polymerization catalyst and which is capable offorming an ionic complex from the transition metal compound of thecomponent (A) or its derivative include (B-1) an ionic compound forreacting with the transition metal compound of the component (A) to forman ionic complex, (B-2) an aluminoxane, and (B-3) a Lewis acid.

As the ionic compound of the component (B-1), any ionic compound can beused, so far as it reacts with the transition metal compound of thecomponent (A) to form the ionic complex. However, there can be suitablyused a compound comprising a cation and an anion in which a plurality ofgroups are bonded to an element, particularly a coordinate complexcompound comprising a cation and an anion in which a plurality of groupsare bonded to an element. The compound comprising a cation and an anionin which a plurality of groups are bonded to an element is a compoundrepresented by the general formula

([L¹-R¹⁶]^(k+))_(i)([M⁴Z¹Z² . . . Z^(n)]^((h-g)-))_(j)  (XVI)

or

([L²]^(k+))_(i)([M⁵Z¹Z² . . . Z^(n)]^((h-g)-))_(j)  (XVII)

wherein L² is M⁶, R¹⁷R¹⁸M⁷, R¹⁹ ₃C or R²⁰M⁷.

[in the formulae (XVI) and (XVII), L¹ is a Lewis base; M⁴ and M⁵ areeach an element selected from the groups 5, 6, 7, 8-10, 11, 12, 13, 14and 15 of the periodic table, preferably an element selected from thegroups 13, 14 and 15; M⁶ and M⁷ are each an element selected from thegroups 3, 4, 5, 6, 7, 8-10, 1, 11, 2, 12 and 17 of the periodic table;Z¹ to Z^(n) are each a hydrogen atom, a dialkylamino group, an alkoxygroup having 1 to 20 carbon atoms, an aryloxy group having 6 to 20carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group,an alkylaryl group or an arylalkyl. group having 6 to 20 carbon atoms, ahalogen-substituted hydrocarbon having 1 to 20 carbon atoms, an acyloxygroup having 1 to 20 carbon atoms, an organic metalloid group or ahalogen atom, and Z¹ to Z^(n) may bond to each other to form a ring. R¹⁶is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or anaryl group, an alkylaryl group or an arylalkyl group having 6 to 20carbon atoms; R¹⁷ and R¹⁸ are each a cyclopentadienyl group, asubstituted cyclopentadienyl group, an indenyl group or a fluorenylgroup; and R¹⁹ is an alkyl group having 1 to 20 carbon atoms, an arylgroup, an alkylaryl group or an arylalkyl group. R²⁰ is a large cyclicligand such as tetraphenylporphyrin or phthalocyanine. g is a valence ofeach of M⁴ and M⁵, and it is an integer of 1 to 7; h is an integer of 2to 8; k is an ion valence of [L¹-R¹⁶] or [L²] and it is an integer of 1to 7; and p is an integer of 1 or more, and j=(i×k)/(h−g).

Here, typical examples of the Lewis base represented by the L¹ includeammonia, amines such as methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, tri-n-butylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline andp-nitro-N,N-dimethylaniline, phosphines such as triethylphosphine,triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether,diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethylthioether and tetrahydrothiophene, and an ester such as ethyl benzoate.

Furthermore, typical examples of M⁴ and M⁵ include B, Al, Si, P, As andSb, and B and P are preferable. Typical examples of M⁶ include Li, Na,Ag, Cu, Br and I, and typical examples of M⁷ include Mn, Fe, Co, Ni andZn. Typical examples of Z¹ to Z^(n) include a dimethylamino group and adiethylamino group as the dialkylamino group; a methoxy group, an ethoxygroup and an n-butoxy group as the alkoxy group having 1 to 20 carbonatoms; a phenoxy group, a 2,6-dimethylphenoxy group and a naphthyloxygroup as the aryloxy group having 6 to 20 carbon atoms; a methyl group,an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,an n-octyl group and a 2-ethylhexyl group as the alkyl groups having 1to 20 carbon atoms; a phenyl group, a p-tolyl group, a benzyl group, a4-t-butylphenyl. group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenylgroup, a 2,4-dimethylphenyl group and a 2,3-dimethylphenyl group as thearyl groups, alkylaryl groups or arylalkyl groups having 6 to 20 carbonatoms; a p-fluorophenyl group, a 3,5-difluorophenyl group, apentachlorophenyl group, a 3,4,5-trifluorophenyl group, apentafluorophenyl group and a 3,5-di(trifluoromethyl)phenyl group as thehalogen-substituted hydrocarbons having 1 to 20 carbon atoms; F, Cl, Brand I as the halogen atoms; and a pentamethylantimony group, atrimethylsilyl group, a trimethylgermil group, a diphenylarsine group, adicyclohexylantimony group and a diphenylboron group as the organicmetalloid groups. Typical examples of R¹⁶, R¹⁹ are as mentioned above.Typical examples of the substituted cyclopentadienyl group of R¹⁷ andR¹⁸ include alkyl group-substituted groups such as amethylcyclopentadienyl group, a butylcyclopentadienyl group and apentamethylcyclopentadienyl group. Here, the alkyl group usually has 1to 6 carbon atoms, and the number o:f the substituted alkyl groups is aninteger of 1 to 5.

Among the compounds represented by the general formulae (XVI) and(XVII), the compounds in which M⁴ and M⁵ are boron are preferable.

Examples of the compound of the general formula (XVI) includetriethylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, trimethylammonium tetraphenylborate,tetraethylammonium tetraphenylborate, methyl-tri(n-butyl)ammoniumtetraphenylborate, benzyltri(n-butyl)ammonium tetraphenylborate,dimethyldiphenylammonium tetraphenylborate, methyltriphenylammoniumtetraphenylborate, trimethylanilinium tetraphenylborate,methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium) tetraphenylborate, trimethylsulfoniumtetraphenylborate, benzylmethylsulfonium tetraphenylborate,triethylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetrabutylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, [methyltri(n-butyl)ammonium]tetrakis(pentafluorophenyl)borate, [benzyltri(n-butyl)ammonium]tetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, methyltriphenylammoniumtetrakis(pentafluorophenyl)borate, dimethyldiphenylammoniumtetrakis(pentafluorophenyl)borate, aniliniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylaniliniumtetrakis(pentafluorophenyl)borate, dimethyl(m-nitroanilinium)tetrakis(pentafluorophenyl)borate,dimethyl(p-bromoanilinium)tetrakis(pentafluorophenyl)borate, pyridiniumtetrakis(pentafluorophenyl)borate, (4-cyanopyridinium)tetrakis(pentafluorophenyl)borate, (N-methylpyridinium)tetrakis(pentafluorophenyl)borate, (N-benzylpyridinium)tetrakis(pentafluorophenyl)borate, (2-cyano-N-methylpyridinium)tetrakis(pentafluorophenyl)borate, (4-cyano-N-methylpyridinium,tetrakis(pentafluorophenyl)borate, (4-cyano-N-benzylpyridinium)tetrakis(pentafluorophenyl)borate, trimethylsulfoniumtetrakis(pentafluorophenyl)borate, benzyldimethylsulfoniumtetrakis(pentafluorophenyl)borate, tetraphenylphosphoniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, dimethylaniliniumtris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,triethylammoniumtris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,pyridiniumtris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,(N-methylpyridinium)tris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,(2-cyano-N-methylpyridinium)tris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,(4-cyano-N-benzylpyridinium)tris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,triphenylphosphoniumtris(pentafluorophenyl)(p-trifluoromethyltetrafluorophenyl)borate,dimethylaniliniumtris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,triethylammoniumtris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate, pyridiniumtris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,(N-methylpyridinium)tris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,(2-cyano-N-methylpyridinium)tris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,(4-cyano-N-benzylpyridinium)tris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,triphenylphosphoniumtris(pentafluorophenyl)(2,3,5,6-tetrafluoropyridinyl)borate,dimethylanilinium tris(pentafluorophenyl)(phenyl)borate,dimethylaniliniumtris(pentafluorophenyl)[3,5-di(trifluoromethyl)phenyl]borate,dimethylaniliniumtris(pentafluorophenyl)(4-trifluoromethylphenyl)borate,dimethylanilinium triphenyl(pentafluorophenyl)borate andtriethylammonium hexafluoroarsenate.

On the other hand, examples of the compound of the general formula(XVII) include ferrocenium tetraphenylborate, silver tetraphenylborate,trityl tetraphenylborate, tetraphenylporphyrinmanganesetetraphenylborate, ferrocenium tetrakis(pentafluorophenyl)borate,(1,1′-dimethylferrocenium) tetrakis(pentafluorophenyl)borate,decamethylferrocenium tetrakis(pentafluorophenyl)borate,acetylferrocenium tetrakis(pentafluorophenyl)borate, formylferroceniumtetrakis(pentafluorophenyl)borate, cyanoferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, tetraphenylporphyrinmanganesetetrakis(pentafluorophenyl)borate, tetraphenylporphyriniron chloridetetrakis(pentafluorophenyl)borate, tetraphenylporphyrinzinctetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silverhexafluoroarsenate and silver hexafluoroantimonate.

The ionic compounds, which are the components (B-1), capable of reactingwith the transition metal compound of the above-mentioned component (A)to form an ionic complex may be used singly or in a combination of twoor more thereof. Furthermore, a component comprising the transitionmetal compound of the component (A) and the ionic compound, which is thecomponent (B-1), capable of forming an ionic complex may be apolycationic complex.

On the other hand, as the aluminoxane of the component (B-2), there canbe mentioned a chain aluminoxane represented by the general formula(XVIII)

(wherein R²¹s are each independently a hydrocarbon group such as analkyl group, a cycloalkyl group, an alkenyl group, an aryl group or anarylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbonatoms, or a halogen atom, more preferably the alkyl group; and f denotesa polymerization degree, and it is an integer of usually 2 to 50,preferably 2 to 40),

and a cyclic aluminoxane represented by the general formula (XIX)

(wherein R²¹s are as defined above; and f is usually an integer of 3 to50, preferably 3 to 40).

Furthermore, modified aluminoxanes can also suitably be used which canbe obtained by modifying the aluminoxanes represented by the generalformulae (XVIII) and (XIX) with a compound such as water having anactive hydrogen and which are insoluble in usual solvents.

As a preparation method of the above-mentioned aluminoxanes, a methodcan be mentioned in which an alkylaluminum is brought into contact witha condensation agent such as water, but no particular restriction is puton its means, and the reaction can be carried out in a known manner. Forexample, there are (1) a method which comprises dissolving an organicaluminum compound in an organic solvent, and then bringing the solutioninto contact with water, (2) a method which comprises first adding anorganic aluminum compound at the time of polymerization, and then addingwater, (3) a method which comprises reacting water of crystallizationcontained in a metallic salt or water adsorbed by an inorganic substanceor an organic substance with an organic aluminum compound, and (4) amethod which comprises reacting a tetraalkyldialuminoxane with atrialkylaluminum, and further reacting with water.

These aluminoxanes may be used singly or in a combination of two or morethereof.

Furthermore, no particular restriction is put on the Lewis acid which isthe (B-3) component, and this Lewis acid may be an organic compound or asolid inorganic compound. As the organic compound, boron compounds andaluminum compounds are preferably used, and as the inorganic compound,magnesium compounds and aluminum compounds are preferably used. Examplesof the organic aluminum compounds includebis(2,6-di-t-butyl-4-methylphenoxy)aluminum methyl and(1,1-bi-2-naphthoxy)aluminum methyl, examples of the magnesium compoundsinclude magnesium chloride and diethoxymagnesium, examples of thealuminum compounds include aluminum oxide and aluminum chloride, andexamples of the boron compounds include triphenylboron,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,tris[(4-fluoromethyl)phenyl]boron, trimethylboron, triethylboron,tri-n-butylboron, tris(fluoromethyl)boron, tris(pentafluoroethyl)boron,tris(nonafluorobutyl)boron, tris(2,4,6-trifluorophenyl)boron,tris(3,5-difluoro)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,bis(pentafluorophenyl)fluoroboron, diphenylfluoroboron,bis(pentafluorophenyl)chloroboron, dimethylfluoroboron,diethylfluoroboron, di-n-butylfluoroboron,pentafluorophenyldifluoroboron, phenyldifluoroboron,pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboronand n-butyldifluoroboron. These Lewis acids may be used singly or in acombination of two or more thereof.

In the present invention, the above-mentioned components (B-1), (B-2)and (B-3) may be used singly or in a combination of two or more thereofas the catalytic component (B).

In the polymerization catalyst which can be used in the presentinvention, if necessary, as the component (C), there can be used anorganic aluminum compound represented by the general formula (XX)

R²² _(m)AlQ_(3-m)  (XX)

(wherein R²² represents an alkyl group having 1 to 10 carbon atoms; Q isa hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms or a halogen atom, and m is an integerof 1 to 3).

In particular, when as the component (B), the ionic compound representedby the component (B-1), capable of reacting with the transition metalcompound of the component (A) to form an ionic complex, is used togetherwith the organic aluminum compound (C), a high activity can be obtained.

Typical examples of the compound represented by the general formula (XX)include trimethylaluminum, triethylaluminum triisopropylaluminum,triisobutylaluminum, dimethylaluminum chloride, diethylaluminumchloride, methylaluminum dichloride, ethylaluminum dichloride,dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminumhydride and ethylaluminum sesquichloride.

These organic aluminum compounds may be used singly or in a combinationof two or more thereof.

Next, in the present invention, at least one of the catalyst components(A), (B) and, if desired, (C) can be supported on a suitable carrier andthen used.

No particular restriction is put on the kind of carrier, and inorganicoxide carriers, other inorganic carriers and organic carriers all can beused, but the inorganic oxide carriers and the other inorganic carriersare particularly preferable.

Typical examples of the inorganic oxide carriers include SiO₂, A1₂0₃,MgO, ZrO₂, TiO₂, Fe₂O₃, B₂0₃, CaO, ZnO, BaO, ThO₂ and mixtures thereof,for example, silica-alumina, zeolite, ferrite, sepiolite and glassfiber. Above all, SiO₂ and Al₂O₃ are particularly preferable. In thisconnection, the above-mentioned inorganic oxide carrier may contain asmall amount of a carbonate, a nitrate, a sulfate or the like.

On the other hand, examples of the inorganic carriers other thanmentioned above include magnesium compounds such as MgCl₂ and Mg(OC₂H₅)₂and their complex salts as well as organic magnesium compoundsrepresented by the general formula MgR²³ X³Y. Here, R²³ represents analkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms or an aryl group having 6 to 20 carbon atoms; X³ is ahalogen atom or an alkyl group having 1 to 20 carbon atoms; x is 0 to 2;and y is 0 to 2.

Furthermore, examples of the organic carriers include polymers such aspolystyrenes, styrene-divinylbenzene copolymers, substitutedpolystyrenes, polyethylenes, polypropylenes and polyarylates, starch andcarbon.

The state of the carrier which can be used herein depends upon its kindand a manufacturing process, but its average particle diameter isusually in the range of 1 to 300 μm, preferably 10 to 200 μm, morepreferably 20 to 100 μm.

If the particle diameter is small, the fine powder of the polymerincreases, and if the particle diameter is large, the coarse particlesof the polymer increase, which causes the deterioration of a bulkdensity and the clogging of a hopper.

Moreover, the specific surface area of the carrier is usually in therange of 1 to 1000 m²/g, preferably 50 to 500 m²/g, and its pore volumeis usually in the range of 0.1 to 5 cm³/g, preferably 0.3 to 3 cm³/g.

If either of the specific surface area and the pore volume deviates fromthe above-mentioned range, a catalyst activity deteriorates sometimes.In this connection, the specific surface area and the pore volume can becalculated from the volume of an adsorbed nitrogen gas in accordancewith a BET method (refer to Journal of the American Chemical Society,Vol. 60, p. 309 (1983)].

Furthermore, it is desirable that the above-mentioned carrier, whenused, is calcined usually at 150 to 1000° C., preferably 200 to 800° C.

No particular restriction is put on a method for supporting thecatalytic components on the carrier, and a conventional usual method canbe used.

Next, a ratio between the respective catalytic components which can beused in the present invention will be described. In the case (1) thatthe catalytic components (A) and (B-1) are used, both the components aresuitably used so that a molar ratio of the component (A)/the component(B-1) may be in the range of 1/0.1 to 1/100, preferably 1/0.5 to 1/10,more preferably 1/1 to 1/5. In the case (2) that the catalyticcomponents (A), (B-1) and (C) are used, a molar ratio of the component(A)/the component (B-1) is the same as in the above-mentioned case (1),but a molar ratio of the component (A)/the component (C) is in the rangeof 1/2,000 to 1/1, preferably 1/1,000 to 1/5, more preferably 1/500 to1/10.

Furthermore, in the case (3) that the catalytic components (A) and (B-2)are used, both the components are suitably used so that a molar ratio ofthe component (A)/the component (B-2) may be in the range of 1/10 to1/10,000, preferably 1/20 to 1/5,000, more preferably 1/30 to 1/2,000.In the case (4) that the catalytic components (A), (B-2) and (C) areused, a molar ratio of the component (A)/the component (B-2) is the sameas in the above-mentioned case (3), but a molar ratio of the component(A)/the component (C) is in the range of 1/2,000 to 1/1, preferably1/1,000 to 1/2, more preferably 1/500 to 1/5.

In addition, in the case (5) that the catalytic components (A) and (B-3)are used, both the components are suitably used so that a molar ratio ofthe component (A)/the component (B-3) may be in the range of 1/0.1 to1/2,000, preferably 1/0.2 to 1/1,000, more preferably 1/0.5 to 1/500. Inthe case (6) that the catalytic components (A), (B-3) and (C) are used,a molar ratio of the component (A)/the component (B-3) is the same as inthe above-mentioned case (5), but a molar ratio of the component (A)/thecomponent (C) is in the range of 1/2,000 to 1/1, preferably 1/1,000 to1/5, more preferably 1/500 to 1/10.

No particular restriction is put on a polymerization method forobtaining the branched ethylenic macromonomer and the copolymer of thepresent invention, and examples of the utilizable polymerization methodinclude a solvent polymerization method (suspension polymerization andsolution polymerization) using an inactive hydrocarbon or the like, abulk polymerization method in which the polymerization is carried outunder substantially inactive hydrocarbon-free conditions, and a gaseousphase polymerization.

Examples of the hydrocarbon solvent which can be used in thepolymerization include saturated hydrocarbons such as butane, pentane,hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane,aromatic hydrocarbons such as benzene, toluene and xylene, andchlorine-containing solvents such as chloroform, dichloromethane,ethylene dichloride and chlorobenzene.

Polymerization temperature is usually in the range of −100 to 200° C.,preferably −50 to 100° C., more preferably 0 to 100° C., andpolymerization pressure is usually in the range of atmospheric pressureto 100 kg/cm²G, preferably atmospheric pressure to 50 kg/cm²G, morepreferably atmospheric pressure to 20 kg/cm²G.

When the branched ethylenic macromonomer is prepared, the control of amolecular weight can be carried out by a usual manner of lowering themolecular weight, for example, a manner of raising the temperature, amanner of decreasing the amount of the monomer to be fed, a manner ofincreasing the amount of the catalyst, or the like. Furthermore, whenthe copolymer is prepared, the control of the molecular weight of theobtained polymer is carried out by a usual means, for example, (1)hydrogen, (2) temperature, (3) a monomer concentration or (4) a catalystconcentration.

Furthermore, the present invention is also directed to a substantiallyunsaturated group-free branched ethylenic polymer obtained byhydrogenating the branched ethylenic macromonomer. No particularrestriction is put on this hydrogenation method, and the macromonomer ishydrogenated in the presence of a known hydrogenation catalyst to obtainthe desired substantially unsaturated group-free branched ethylenicpolymer. This hydrogenated branched ethylenic polymer is useful as a waxin various uses such as a base oil for a lubricating oil and an additivehaving a controlled viscosity index.

No particular restriction is put on the kind of hydrogenation catalystwhich can be used herein, and there can be employed the catalystspreviously mentioned in detail and catalysts which can usually be usedat the time of the hydrogenation of an olefin compound. For example, thefollowing catalysts can be mentioned.

Examples of a heterogeneous catalyst include nickel, palladium andplatinum as well as solid catalysts obtained by supporting these metalsonto carriers such as carbon, silica, diatomaceous earth, alumina andtitanium oxide, for example, nickel-silica, nickel-diatomaceous earth,palladium-carbon, palladium-silica, palladium-diatomaceous earth andpalladium-alumina. Examples of the nickel catalyst include Raney nickelcatalysts, and examples of the platinum catalyst include a platinumoxide catalyst and platinum black. Examples of a homogeneous catalystinclude catalysts containing metals in the groups 8 to 10 of theperiodic table as basic components, for example, catalysts comprising Niand Co compounds and organic metallic compounds of metals selected fromthe groups 1, 2 and 3 of the periodic table such as cobaltnaphthenate-triethylaluminum, cobalt octenoate-n-butyl-lithium, nickelacetylacetonato-triethylaluminum, and Rh compounds.

In addition, Ziegler hydrogenation catalysts disclosed by M. S. Saloanet al. [J. Am. Chem. Soc., 85, p. 4014 (1983)] can also effectivelyused. Examples of the:se catalysts include the following compounds.

Ti(O—iC₃H₇)₄—(iC₄H₉)₃Al,

Ti(O—iC₃H₇)₄—(C₂H₅)₃Al,

(C₂H₅)₂TiCl₂—(C₂H₅)₃Al,

Cr(acac)₃—(C₂H₅)₃Al

(wherein acac represents acetylacetonato),

Na(acac)—(iC₄H₉)₃Al,

Mn(acac)₃—(C₂H₅)₃Al,

Fe(acac)₃—(C₂H₅)₃Al,

Ca(acac)₂—(C₂H₅)₃Al, and

(C₇H₅COO)₃Co—(C₂H₅)₃Al.

The amount of the catalyst to be used in the hydrogenation step issuitably selected so that a molar ratio of the remaining unsaturatedgroups to the hydrogenation catalyst components in the macromonomer maybe in the range of 107:1 to 10:1, preferably 106:1 to 102:1.

Furthermore, the charge pressure of hydrogen is suitably in the range offrom atmospheric pressure to 50 kg/cm²G. Besides, a reaction temperatureis preferably on a higher side in the range in which the macromonomer donot decompose, and it is usually selected in the range of −100 to 300°C., preferably −50 to 200° C., more preferably 10 to 180° C.

Next, the present invention will be described in more detail withreference to examples, but the scope of the present invention should notbe limited to these examples.

EXAMPLE 1

(1) Preparation of methylaluminoxane

In a 500-ml glass container which had been purged with argon were placed200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate(CUSO₄.5H₂O) and 24 ml (250 mmol) of trimethylaluminum, and the mixturewas then reacted at 40° C. for 8 hours. Afterward, solid components wereremoved from the reaction mixture to obtain a toluene solutioncontaining methylaluminoxane.

(2) Preparation of macromonomer

A 2-liter three-necked flask was purged with ethylene, and in this flaskwere placed 1,000 ml of toluene, 4 mmol of triisobutylaluminum (TIBA),80 mmol of methylaluminoxane prepared in the above-mentioned (1) interms of an aluminum atom and 0.3 mmol ofpentamethylcyclopentadienyltitanium trimethoxide, and ethylene wascontinuously fed at 40° C. under atmospheric pressure to carry outpolymerization for 10 hours. After the completion of the polymerization,a small amount of methanol was poured thereinto, and demineralizationwas then done with an aqueous hydrochloric acid/toluene system, followedby fractionation. The resulting toluene layer was dried over anhydroussodium sulfate, and toluene was then distilled off to obtain 3.5 g of awaxy product.

(3) Evaluation of macromonomer

(1) Results of ¹H-NMR measurement (CDCl₃, 50° C.)

A molar ratio of a terminal methyl group/a vinyl group was 8/1, and thecontent of the vinyl group was 90 mol % with respect to the totalunsaturated groups.

(2) Results of ¹³C-NMR measurement (CDC1₃, 50° C.)

As the peaks of a methyl group, there were an ethyl branch at 10.5 to11.0 ppm, a butyl or more branch at 13.5 to 14.0 ppm and a methyl branchat 19.0 to 20.0 ppm, and with regard to a peak intensity ratio, themethyl branch:the ethyl branch:the butyl or more branch was 2:1:4.

Furthermore, from the peak intensity of a methylene group adjacent tothe methyl group, it was apparent that the butyl branch:a hexyl or morebranch (molar ratio) was 1:3, whereby it was confirmed that the productwas a macromonomer having a structure in which the methyl branch:theethyl branch:the butyl branch:the hexyl or more branch (molar ratio) was2:1:1:3.

(3) Measurement of weight-average molecular weight

The molecular weight of the macromonomer was measured in terms of thepolyethylene under conditions of device: Waters ALC/GPC 150C, column:made by Toso Co., Ltd., TSK HM+GMH6×2, solvent: 1,2,4-trichlorobenzene,temperature: 135° C., flow rate: 1 ml/min by a gel permeationchromatography (GPC) method. As a result, the weight-average molecularweight (Mw) of the macromonomer was 3,300.

EXAMPLE 2

Under a nitrogen atmosphere, 0.2 g of the branched macromonomer obtainedin Example 1-(2) was dissolved in 50 ml of toluene. Next, 0.5 mmol oftriisobutylaluminum was added to the solution, and nitrogen was thenexchanged for ethylene and it was fed under atmospheric pressure whilethe solution was stirred.

Furthermore, 20 micromol of anilinium tetrakis(pentafluorophenyl)borateand 10 micromol of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride were added thereto, and polymerization was then carried outat 90° C. for 30 minutes under atmospheric pressure while ethylene wasallowed to flow. Next, in order to remove the unreacted macromonomer,the reaction solution was sufficiently washed at room temperature withtoluene to obtain 3.7 g of an ethylenic copolymer.

The intrinsic viscosity of this copolymer measured in decalin at atemperature of 135° C. was in the range of 2.6 dl/g, and in the ¹³C-NMRof the copolymer, there were observed absorptions attributed to an ethylbranch at 10.5 ppm, a butyl or more branch at 13.5 ppm and a methylbranch at 19.5 ppm which were confirmed in the macromonomer.

Furthermore, a CH₃/CH₂ molar ratio calculated from ¹H-NMR was 1/186.

EXAMPLE 3

The macromonomer obtained in Example 1-(2) was hydrogenated in a decalinsolution under conditions of a temperature of 140° C., a reaction timeof 6 hours, a macromonomer concentration of 0.1% by weight, a hydrogenpartial pressure of 30 kg/cm²G and a ruthenium-supporting carbon carriercatalyst (Ru content=5% by weight) concentration of 4% by weight, andthe resulting polymer was then isolated from a reaction solution.

According to the results of ¹H-NMR analysis of this polymer, anyabsorption of an unsaturated group was not observed.

EXAMPLE 4

In a 1.4-liter autoclave equipped with a stirrer were placed 500 ml ofdehydrated toluene, and 4 mmol (as an aluminum atom) of themethylaluminoxane prepared in Example 1-(1) and 1 g of the macromonomerobtained in Example 1-(2) were then added thereto. After stirring anddissolving, 0.01 mmol of (2,2 -dimethylsilylene)-bis(indenyl)zirconiumdichloride was added, and the solution was heated up to 50° C. Next,propylene was introduced into the autoclave, and polymerization wascarried out for 1 hour while the state of 6.0 kg/cm²G was maintained.After the completion of the polymerization, the gaseous phase waspurged, and the slurry portion was collected by filtration and thendried to obtain 35 g of a powdery propylene copolymer.

The intrinsic viscosity of this copolymer measured in decalin at 135° C.was 0.8 dl/g, and in the ¹³C-NMR measurement of the copolymer, therewere observed absorptions attributed to an ethyl branch at 10.5 ppm anda butyl or more branch at 13.5 ppm which were confirmed in themacromonomer. Furthermore, the content of the macromonomer segmentcalculated from ¹H-NMR was 0.2% by weight. In addition, the meltingpoint of the copolymer measured by a DSC (a differential scanningcalorimeter) was 142.5° C., and the weight-average molecular weight(Mw)/the number-average molecular weight (Mn) of the copolymer was 2.6.

EXAMPLE 5

(1) Preparation of methylaluminoxane

Toluene was distilled off from the toluene solution of themethylaluminoxane prepared in Example 1-(1), and the resulting solidcomponent was then treated at 130° C. under a reduced pressure of 3×10⁻³Torr for 5 hours. This solid component was dissolved in toluene again toprepare the toluene solution of methylaluminoxane.

(2) Preparation of styrene-macromonomer copolymer

In a 1.4-liter autoclave equipped with a stirrer were placed 500 ml ofdehydrated toluene. Furthermore, 5 mmol (as an aluminum atom) of themethylaluminoxane prepared in the above-mentioned (1), 1 g of themacromonomer obtained in Example 1-(2), 0.03 mmol ofpentamethylcyclopentadienyltitanium tributoxide and 200 ml of styrenewere then added thereto, and copolymerization was carried out at 80° C.under 6.0 kg/cm²G for 2 hours. After the completion of thepolymerization, the reaction mixture was poured into a large amount ofmethanol, and the solid portion was collected by filtration and thendried to obtain 30 g of a copolymer.

The intrinsic viscosity of this copolymer measured in decalin at 135° C.was 0.8 dl/g, and in the ¹³C-NMR measurement of the copolymer, therewere observed absorptions attributed to an ethyl branch at 10.5 ppm anda butyl or more branch at 13.5 ppm which were confirmed in themacromonomer. Furthermore, the content of the macromonomer segmentcalculated from ¹H-NMR was 0.1% by weight. In addition, the meltingpoint of the copolymer measured by a DSC was 265° C., and theweight-average molecular weight (Mw)/the number-average molecular weight(Mn) of the copolymer was 2.2.

EXAMPLE 6

Preparation of(1,1′-dimethylsilylene)(2,2′-isopropylidene)-(indenyl)zirconiumdichloride

(1) In a 1-liter three-necked flask purged with nitrogen were placed10.8 g of magnesium and 45 ml of THF, and 0.6 ml of dibromomethane wasadded dropwise thereto. After stirring for 5 minutes, the solvent wasdistilled off under reduced pressure, and 200 ml of THF was then newlyadded. Next, 18.3 g (0.105 mol) of α,α′-dichloro-o-xylene was dissolvedin 300 ml of THF, and the solution was then added dropwise to theautoclave at room temperature over 3 hours. After the completion of thedropping, the solution was further stirred for 15 hours and cooled to−78° C., and a THF (100 ml) solution containing 6.8 g (36.2 mmol) ofdiethyl dimethylmalonate was added dropwise over 1 hour. Afterward, thetemperature of the solution was returned to room temperature, and afterstirring for 2 hours, 100 ml of water was added thereto at roomtemperature. The mixture was filtered with suction, and the solvent wasthen distilled off under reduced pressure. Next, extraction was carriedout by the use of dichloromethane and a 1N aqueous ammonium chloridesolution, and the resulting organic layer was washed twice with water,and then dried over magnesium sulfate. The solid was removed byfiltration, and the solvent was then distilled off to obtain a yellowoil. In addition, the oil was purified through a column chromatographusing active alumina, and then recrystallized from hexane to obtain 4.8g of (15.9 mmol, yield=44%) the desired compound (the following compounda) in the state of a colorless crystal.

The ¹H-NMR of the obtained compound was measured, and the followingresults were obtained.

¹H-NMR (CDCl₃, 6): 1.235 (s, 6H, CH₃), 3.002 (d, J=16.4 Hz) and 3.470(d, J=16.4 Hz) (8H, CH₂), 3.767 (s, 2H, OH), 7.2-7.4 (mul, 8H, PhH)

Compound a

wherein Me is a methyl group, and the same shall apply hereinafter.

(2) 4.8 g (15.9 mol) of the compound a obtained in the above-mentioned(1) was dissolved in 30 ml of dichloromethane, and 3.04 g (15.9 mmol) ofp-toluenesulfonic acid was added, followed by reflux for 8 hours. Thereaction mixture was washed with an aqueous sodium hydrogen-carbonatesolution and water, and then dried over magnesium sulfate. The resultingprecipitate was removed by filtration, and the solvent was thendistilled off to obtain a yellow oil. This oil was purified through acolumn chromatograph using silica gel, and then recrystallized fromhexane to obtain 2.3 g (8.6 mmol, yield=54%) of the desired compound(the following compound b) in the state of a colorless crystal.

The ¹H-NMR of the obtained compound was measured, and the followingresults were obtained.

¹H-NMR (CDCl₃, δ): 1.586 (s, 6H, CH₃), 3.470 (s, 4H, CH₂), 3.767 (s, 2H,CpH) 6.9-7.5 (mul, 8H, PhH)

Compound b

(3) In a Schlenk tube purged with nitrogen were placed 6.2 g (22.7 mmol)of the Compound b obtained by repeating the reactions of theabove-mentioned (1) and (2) and 50 ml of diethyl ether. Next, thesolution was cooled to −78° C., and 28.4 ml (45.4 mmol) of ann-butyllithium solution having a concentration of 1.6 mol/liter wasadded dropwise thereto. The temperature of the solution was returned toroom temperature, and at this time, a white precipitate was graduallydeposited. After stirring at room temperature for 3 hours, thesupernatant liquid was drawn out, and the precipitate was washed twicewith a small amount of diethyl ether. Next, the precipitate was driedunder reduced pressure to obtain a dilithium salt (the followingCompound c) in the state of a colorless powder:

Compound c

(4) The dilithium salt (Compound c) obtained above was dissolved in 100ml of THF. Next, 3.0 g (22.7 mmol) of distilled dichlorodimethylsilanewas slowly added dropwise at room temperature, followed by stirring for3 hours. The solvent was distilled off, and extraction was then carriedout with dichloromethane and water. The resultant organic layer waswashed twice with water, and then dehydrated over magnesium sulfate.Afterward, the resulting precipitate was filtered, and recrystallizationwas then carried out from hexane to obtain 6.5 g (19.6 mmol, yield:86.5%) of a colorless crystal (the following Compound d).

The ¹H-NMR of this product was measured, and the following results wereobtained.

¹H-NMR (CDCl₃, δ): −0.354 (s, 6H, SiCH₃), 1.608 (s, 6H, CCH₃), 3.347 (s,2H, SiCH), 6.785 (s, 2H, CpH), 6.9-7.6 (mul, 8H, PhH)

Compound d

(5) In a Schlenk tube purged with nitrogen were placed 0.9 g (2.7 mmol)of the Compound d obtained in the above-mentioned (4) and 50 ml ofhexane. Next, the solution was cooled to 0° C., and 3.4 ml (5.4 mmol) ofan n-butyllithium solution having a concentration of 1.6 mol/liter wasadded dropwise thereto. The temperature of the solution was returned toroom temperature, and at this time, a white precipitate was deposited.After stirring at room temperature for 3 hours, the supernatant liquidwas drawn out, and the precipitate was washed twice with hexane. Next,the precipitate was dried under reduced pressure to obtain a dilithiumsalt (the following Compound e) in the state of a pink powder:

Compound e

(6) Toluene was added to the dilithium salt (Compound e) obtained in theabove-mentioned (5) to form a suspension. Next, to this suspension, atoluene suspension containing 630 mg (2.7 mmol) of tetrachlorozirconiumwas added dropwise at 0° C. The temperature of the mixture was returnedto room temperature, and after stirring for 24 hours, a precipitate wasremoved by filtration and the solution was then concentrated. Afterward,recrystallization was done from toluene-hexane to obtain 240 mg (0.508mmol, yield: 19%) in the state of a yellowish orange crystal.

The ¹H-NMR of this product was measured, and the following results wereobtained.

¹H-NMR (heavy THF, δ): −0.172 (s, 3H, SiCH₃), 0.749 (s, 3H, SiCH₃),1.346 (s, 3H, CCH₃), 2.141 (s, 3H, CCH₃), 3.654 (, 2H, CpH), 6.692 (s,2H, CpH), 6.9-8.1 (mul, 8H, PhH)

Zirconium complex

(7) Preparation of ethylenic macromonomer

In a 1-liter autoclave heated and dried under reduced pressure wereplaced 500 ml of hexane under an argon atmosphere, and its temperaturewas then raised up to 150° C. Next, argon was introduced thereinto until11 kg/cm²G had been reached, and ethylene was then introduced so as toattain a total pressure of 24 kg/cm²G. Afterward, 20 ml of toluene, 10mmol of the methylaluminoxane obtained in Example 1-(1), 0.5 mmol oftriisobutylaluminum and 5 μm of a zirconium complex obtained in theabove-mentioned (6) which had previously been prepared in a feed pipewere fed to the autoclave, and ethylene was then continuously introducedfor 5 minutes so that a total pressure might be constant at 35 kg/cm²G,whereby polymerization was carried out. As a result, 85 g of themacromonomer was obtained.

(8) Evaluation of ethylenic macromonomer

(1) Results of ¹H-NMR measurement

A molar ratio of a terminal methyl group/a vinyl group was 10/1, and thecontent of the vinyl group was 87 mol % with respect to the totalunsaturated groups.

(2) Results of ¹³C-NMR measurement

As the peak of a methyl group, there was a butyl group or more branch at13.5 to 14 ppm, and the peak of a methylene group adjacent to the methylgroup was positioned at 22.8 to 23.0 ppm, whereby it was confirmed thatthe methylene group was a hexyl group or more branch.

(3) Measurement of weight-average molecular weight

The measurement was made as in Example 1-(3), and as a result, theweight-average molecular weight (Mw) of the macromonomer was 5000.

EXAMPLE 7

Preparation of ethylene/1-butene copolymeric macromonomer

The same procedure as in Example 6-(7) was carried out except that afterthe addition of the toluene, 20 g of 1-butene was poured, therebypreparing a copolymer. As a result, 35 g of the macromonomer wasobtained. The evaluation of the macromonomer was carried out as follows.

(1) Results of ¹H-NMR measurement

A molar ratio of a terminal methyl group/a vinyl group was 15/1, and thecontent of the vinyl group was 86 mol % with respect to the totalunsaturated groups.

(2) Results of ¹³C-NMR measurement

As the peak of a methyl group, there was 13.5 to 14 ppm (a butyl groupor more branch), and the peak of a methylene group adjacent to themethyl group was positioned at 22.8 to 23.0 ppm, whereby a hexyl groupor more branch was confirmed.

In addition, as absorptions based on an ethyl branch introduced by theuse of 1-butene, there were confirmed the methyl group at about 11.1 ppmand the methylene group at about 26.8 ppm.

(3) Measurement of weight-average molecular weight

The measurement was made as in Example 1-(3), and as a result, theweight-average molecular weight (Mw) of the macromonomer was 4500.

EXAMPLE 8

(1) Preparation of ethylene/1-butene/macromonomer ternary polymer

In a 1.4-liter autoclave equipped with a stirrer were placed 500 ml ofdehydrated toluene. Furthermore, 4 Mmol (as an aluminum atom) of themethylaluminoxane prepared in the above-mentioned 5-(1), 5 g of themacromonomer obtained in Example 6 and 8 g of 1-butene were addedthereto, followed by sufficient stirring to dissolve the macromonomer.Afterward, the solution was heated up to 65° C., and 0.01 mmol ofpentamethylcyclopentadienyltitanium tributoxide was then added thereto.Immediately, hydrogen was introduced into the autoclave until a gaugepressure of 0.5 kg/cm² had been reached, and ethylene was thencontinuously fed under a gauge pressure of 4 kg/cm². After thecompletion of the polymerization, the pressure was released and thereaction mixture was poured into a large amount of methanol, and thesolid portion was collected by filtration and then dried to obtain 48 gof a copolymer.

The intrinsic viscosity of this copolymer measured in decalin at 135° C.was 1.6 dl/g, and the content of a butene-1 unit was 6.2 mol %. Inaddition, as kinds of branches other than 1-butene, hexyl group or morebranches were observed, so that it was elucidated that the macromonomerwas copolymerized. The content of this macromonomer segment was 0.2% byweight. Furthermore, the weight-average molecular weight (Mw) of thiscopolymer was 86000.

(2) Measurement of die swell ratio of copolymer

A die swell ratio (DR) was measured under the following conditions, andit was 2.4.

In this case, the value of [0.5+0.125×logMw] was 1.12.

<Die swell ratio (D_(R))>

The die swell ratio (DR) was obtained as (D₁/D₀) by measuring a diameter(D₁, mm) of a strand formed by extrusion through a capillary nozzle[diameter (D₀)=1.275 mm, length (L)=51.03 mm, L/D₀=40, and entranceangle=90°) at an extrusion speed of 1.5 mm/min (shear rate=10 sec⁻¹) ata temperature of 190° C. by the use of a capillograph made by Toyo SeikiSeisakusho Co., Ltd., and then dividing this diameter by the diameter ofthe capillary nozzle.

In this connection, the diameter (D₁) of the strand was an average valueof values obtained by measuring long axes and short axes of centralportions of 5 samples having a extruded strand length of 5 cm (a lengthof 5 cm from a nozzle outlet).

(3) Measurement of composition distribution of copolymer

A polymer solution of o-dichlorobenzene whose concentration had beenadjusted to about 6 g/liter at 135° C. was poured, by a constantdelivery pump, into a column having an inner diameter of 10 mm and alength of 250 mm which is filled with Chromosorb PNAN (80/100 mesh) as acolumn filler. The polymer solution was cooled to room temperature at arate of 10° C./hr, so that the polymer was adsorbed and crystallized onthe filler. Afterward, o-dichlorobenzene was fed at a feed rate of 2cc/min under heat-up rate conditions of 20° C./hr. Then, theconcentration of the eluted polymer was measured by an infrared detector(device: 1-A Fox Boro CVF Co., Ltd., cell: CaF₂), whereby thecomposition distribution curve to an elution temperature was obtained.

As a result, the elution temperature (T) of the peak top was 72.5° C.,and a half value width (W) was 23.5° C.

In this connection, a value of [−24.9+2470/T] was 9.2.

EXAMPLE 9

(1) Preparation of(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride (A-1)

0.7 g (3.2 mmol) of(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadiene) wasdissolved in 30 ml of hexane, and 6.48 mmol of n-butyllithium (a hexanesolution containing n-butyllithium of 1.5 mol per liter of hexane) wasadded dropwise at −78° C. to the solution, followed by stirring at roomtemperature for 5 hours. Next, the solvent was distilled off, and theresulting residue was washed with 20 ml of hexane, and the washed whitesolid was then dried under reduced pressure. Afterward, to the toluenesuspension (20 ml) of this solid, 0.8 g (3.2 mmol) of zirconiumtetrachloride was added, and after stirring for 12 hours at roomtemperature, the solvent was distilled off. Next, recrystallization wascarried out from dichloromethane-hexane to obtain 0.3 g of(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)zirconiumdichloride in the state of a light yellow powder.

The ¹H-NMR of this product was measured, and the following results wereobtained.

¹H-NMR (90 MHz, CDCl₃, δ): 1.01 (3H, S, (CH₃)₂Si], 0.54 [3H, S,(CH₃)₂Si], 1.52 [3H, s, (CH₃)₂C], 2.16 [3H, s, (CH₃)₂C], 6.17 (2H, m,—CH—), 6.53 (2H, m, —CH—), 6.82 (2H, m, —CH—).

Incidentally,(1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadiene) wassynthesized in accordance with a procedure described in“Organometallics”, Vol. 10, p. 3739 (1991).

(2) Preparation of macromonomer

A 1-liter three-necked flask was purged with ethylene, and in this flaskwere placed 400 ml of toluene and 1 mmol of triisobutylaluminum (TIBA),followed by heating the solution up to 90° C. Next, ethylene wascontinuously fed to this solution under atmospheric pressure, and aftera saturating state had been attained, 0.02 mmol of the zirconium complexprepared in the above-mentioned (1) and 0.02 mmol ofN,N-dimethylammonium tetrakis(pentafluorophenyl)borate were added to theflask to carry out polymerization for 1 hour. After the completion ofthe polymerization, the reaction mixture was poured into methanol,washed, filtered, and then dried to obtain 43 g of the macromonomer.

(3) Evaluation of macromonomer

The same procedure as in Example 1-(3) was carried out, and as a result,a molar ratio of a terminal methyl group/a vinyl group was 8/1, and thecontent of the vinyl group was 72 mol % with respect to the totalunsaturated groups. In addition, as kinds of branches, hexyl group ormore branches were observed, and the weight-average molecular weight(Mw) of the macromonomer was 2,600.

Possibility of Industrial Utilization

A branched ethylenic macromonomer of the present invention can functionas a comonomer to provide a copolymer having excellent molding andworking properties and can be hydrogenated to provide a branchedethylenic polymer having a low molecular weight as a wax useful invarious uses such as a base oil for a lubricating oil and an additivehaving a controlled viscosity index. Accordingly, the macromonomer canbe considered to be an extremely useful compound.

What is claimed is:
 1. A branched ethylenic macromonomer which isderived from ethylene or derived from ethylene and at least onecomonomer selected from the group consisting of an α-olefin having 3 to20 carbon atoms, acrylic olefin and styrenes, wherein (a) the molarratio of a terminal methyl group to a vinyl group in the macromonomer isin the range of 1 to 100, the macromonomer having a branch other thanthe branch directly derived from the α-olefin, the cyclic olefin or thestyrenes, (b) the ratio of vinyl groups to the total unsaturated groupsin the macromonomer is 70 mol % or more, (c) the weight-averagemolecular weight (Mw) of the macromonomer measured by a gel permeationchromatography is in the range of 100 to 20,000.
 2. A branched ethylenicpolymer substantially in the absence of an unsaturated group which isobtained by hydrogenating the branched ethylenic macromonomer describedin claim
 1. 3. The branched ethylenic macromonomer of claim 1, whereinsaid branch is a short-chain branch whose main chain has 1 to 5 carbonatoms or a long-chain branch whose main chain has 6 or more carbonatoms.
 4. The branched ethylenic macromonomer of claim 1, wherein saidbranch comprises chain having a chain length of 4 or more carbon atoms.5. The branched ethylenic macromonomer of claim 1, wherein said branchcomprises chain having a chain length of 6 or more carbon atoms.
 6. Thebranched ethylenic macromonomer of claim 1, wherein said ratio of vinylgroups to the total unsaturated groups in the macromonomer is 75 mol %or more.
 7. The branched ethylenic macromonomer of claim 1, wherein saidratio of vinyl groups to the total unsaturated groups in themacromonomer is 80 mol % or more.
 8. The branched ethylenic macromonomerof claim 1, wherein said weight-average molecular weight of themacromonomer is in the range of 150 to 18,000.
 9. The branched ethylenicmacromonomer of claim 1, wherein said weight-average molecular weight ofthe macromonomer is in the range of 180 to 16,000.